Manufacture and application of new textile treatment agents



Patented Aug. 15, 1950 MANUFACTURE AND APPLICATION OF NEW TEXTILETREATMENT AGENTS William Baird, Thomas Barr, Arthur Lowe, and JackOliver, Blackley, Manchester, England, assignors to Imperial ChemicalIndustries Limited, a corporation of Great Britain No Drawing.Application July 28,1947, Serial No. 764,258. In Great Britain August14, 1946 15 Claims.

This invention relates to the manufacture of new chemical compounds andto their use in treating textile materials, especially for the purposeof conferring anti-shrink properties on wool.

According to the present invention we manufacture new chemical compoundsof the formula R(-O-CO.NR'-CH2OR")1; where Rstands for an aliphaticradical, substituted or not, B. stands for hydrogen or an organicresidue, R" stands for hydrogen or an alkyl radical and n stands for awhole number greater than 1, from polycarbamates of the formulaR(O-CO-NHR')n by the processes hereinafter set forth;

The polycarbamates which are used as starting materials are derivativesof compounds of the formula R(H)n wherein R and'n have the 7 mentioned,for example, ethylene bis-carbamate,

octadec'ane-l 12-di01 bis-carbamate, trioleinl1:11 :11"-trioltriscarbamate and tristearin 11:1 1' ;'11-triol triscarbamate.

Incarrying the invention into practical effect the pqlycarbamates aremixed with formaldehyde (or witha polymer thereof), advantageously atslightly elevated temperature, for example at 40-60 C., optionally inthe presence of a solvent or diluen, either under alkaline conditions,

whereby the new compounds formed have the formula stated above whereinR," is hydrogen, or under slightly acid conditions in the presence of analcohol, whereby the new compounds formed have the formula stated abovewherein R" is an alkyl radical.

The new compounds, having" the formula stated, wherein R! is an alkylradical may also be made by mixing the halogenomethyl derivative of thepolycarbamate (obtainable for example by treatment of the polycarbamatewith formaldehyde and a hydrogen halide) with an alcohol, advantageouslyat slightly elevated temperatures, for example at 4060'C. or by mixingthe hydroxymethyl derivative of the polycarbamate with an alcohol underslightly acid conditions advantageously at slightly elevatedtemperatures, for example at 40-60 C.

Suitable alcohols for use in the above processes are for example,methyl, ethyl and propyl alcohols, glycol and glycollic acid.

The new compounds are soluble or readily dispersible in water and aresoluble in organic solvents such as alcohols, acetone, benzene, toluene,chloroform, ethylene dichloride and dioxan. When the compounds areheated above C. under acid conditions they decompose,

forming water-insoluble resinous substances.

By a further feature of the invention the new compounds are applied totextile materials which may be of animal or vegetable origin or composedof regenerated cellulose or of cellulose esters or ethers to give themimproved properties including shrink-resistance and/or water-repellency.This feature of the invention comprises impregnating the said textilematerials with a solution or suspension of one or more of the newcompounds in water or in a suitable organic liquid, at a convenienttemperature, for example at a temperature below 160 C., and subsequentlydrying the impregnated material and heating under acid conditions tosuch a temperature that the said new compounds undergo decomposition,for example to a temperature of about C. Acid conditions may be producedby the direct addition of acids themselves or by means of salts of baseswhich liberate acids on heating e. g. pyridine hydrochloride orhydrobromide or by means of heat decomposable quaternary compounds suchas cetoxymethylpyridinium chloride, stearamidomethylpyridinium chloride.

Dispersing agents may be used in the preparation of the impregnatingfluid, for example the condensation product of cetyl alcohol with 1'7molecular proportions of ethylene oxide.

Other textile finishing agents may also be added to the impregnatingfluid. Thus, for example, polyvalent metal salts, for example aluminiumacetate or water-repellent waxes, for example paraffin wax, montan wax,carnauba wax and beeswax, may be added in order to improve thewater-repellent properties of the textile materials.

By a further feature of the invention the new compounds may be appliedin conjunction with compounds which are used to confer creaseresistantproperties on textile materials, for example, condensation products offormaldehyde with phenols or with urea or urea derivatives,

:thetwo treatment agents being applied either Example 1 To a solution of100 parts of the polycarbam-,

ates obtained by treating hydrogenated castor oil with phosgene and thenwith. ammoniasaco sisting essentially of tristearin-ll:11:'11-triotris-carbamate in 240 parts of benzene, .lOparts of paraformaldehyde and20 partsofanhydrous... potassium carbonate are added: Themixtureisstirred at a temperature of 50-6 C.-for.-:2-3-' hours and then filtered.The ,filtrate is evaporated at 45-50 C. under reduced-pressureowhereby7the methylol derivative is obtained as a pale "yel*- low viscous liquid.

Example 2 To. a solution of '7 parts. .of .thepolycarbanh. ates obtainedby treatingcastor .oil with .phos-..

gene and then with. ammonia. consisting. essen: tially oftriolein-ll:11:11"-.triol tris-carbamatev in 120 parts of benzene, 11.4.parts of anhydrous.

potassium carbonate and 5.7. parts of. paraform:

aldehyde are added. The. mixture. is stirred at.

l5-50 -C. for 2 hours. and thenfiltered. The filtrate is concentrated-byevaporation underreduced pressure at ,50-60 C. whereby the methylolderivative is obtained as a clearviscousoil.

I Example 3 1 part of the condensationproductof cety1 a1-.,

coholwith 1'7 molecular.proportions,of,.ethylene oxideis dissolved;in-ZO .parts of .the product of Example 1 and the mixture is emulsifiedwithl'l9 parts of water.

100 parts .of 1.5 N hydrochloric acidare then addedwith stirring. totheemulsion and a light weight wool fiannelis then. padded in theresultant dispersionsqueezed .between.

rubber rollers. toan uptake of approximately 100%, dried at 50 C. andsubsequently. baked at 145- C. for 3 minutes. pared is milled by handfor 15 minutesein 5% The pattern thus pref .45

soap solution in comparison with an.untreated pattern and-shows an. areashrinkage of 11.2%

in comparison with 31.9% material.

Example 4 1 part of the condensation product of cetyl alcohol with 1'!molecular proportions of ethylene" for the untreated oxide is dissolvedin .parts of the product of Example 2 and the mixture is emulsified with'79 parts of water. 100 parts of 2 N hydrochloric acid are then addedwith stirring to the. emulsion and a light weight wool flannel is paddedin thev resultant dispersion, rollers to an uptake of approximately100%, dried at C. and subsequently baked at 145 C. for 3 minutes. Thepattern thus prepared when milled by hand in 5% soap solution for 15minutes squeezed between rubber:

shows an area shrinkage of 2.5% in comparison" with 30.1 for theuntreated material:

Example .5

60 parts of ethylene bis-carbamate are dis-' solved in a mixture of 550parts of water and parts of 37% formaldehyde solution. 5 partsofpotassium carbonate are added and the mixture is stirred at 50 C. for 2hours. Further additionsof" potassium carbonate are made from time-totime-to keep the mixture alkaline to phenolphtha 4 under reducedpressure at 40 C. leaving ethylene bis-hydroxymethylcarbamate as a stiffgum.

Example 6 10 parts of the .methylol derivatives (obtainable asgdescribedin Example 1) of the mixtureof poly carbamates obtained by treatinghydrogenated castor oil with phosgene and then ammonia are dissolved in200 parts of ethanol and a slow .stream.;of .gaseoushydrogen chloride ispassed into the-solution for 10 minutes. The solution is stirred at50-60 C. for 2 hours and then neutralised1by, adding potassiumcarbonate. The mixtureis filtered. and the solvent is removedbyevaporation under reduced pressure at 50-60 C. whereby theethoxymethylcarbamate derivativeis obtained. as a. clear mobile liquid.

Example 7 parts of the chloromethyl derivatives of thepolycarbamatesobtained by treating castor. oil with phosgene. and thenwith ammonia consisting essentially. .of triolein ll:.11':l1"-triol:-tris chloromethyloarbamate. are added with. stirring.during. 1 hourto 400. parts of n-butyl .alco'hol atroomtemperature. Ihemixture is heatedata. 4550".. C. for 4 hours. and is then neutralisedby. the addition of anhydrous .potassium carbonate. The mixture isfiltered: and the. solvent is removed by evaporation under reducedpressure at 50-60.

C. whereby the butoxymethyl caroamate derivative is obtained as a clearmobile. oil.

Example 8 80' parts of the chloromethyl derivatives of Example 1. are.added with stirring during 1 hour to 400. parts of ethylv alcohol atroom temperature. The mixture is heated, at 5060 C. for 8 hours...

and. is .then neutralised by the addition of. anhy.--

evaporationunder reduced pressure at 60 C.

wherebythe ethoxymethylderivative is obtained..-

asa clear mobile oil.

Example 9 10..parts of the methylolderivative of the. poly. carbamatesobtained by treating hydrogenated...

castor oil with .phcsgene and then with ammonia consisting essentiallyof tristearin-1l:11:11,- A "triol-tris-methylolcarbamate are dissolvedin 200 parts of methanol and a slow stream of gaseous... hydrogenchloride is passed throughthe mixture. The mixture is thenheated to for10 minutes. 5090. and stirred at this temperature for 2 hours.

obtained as a clear mobile oil.

We claim: 1

1. As. a new compound, 'tristerin-llrll'xlllftriol .trismethylolcarbomate- 2. .As a new compound. triolein-11:11:11f'-.;.trio1-trissmethylolcarbamate.

3. New chemical compounds :of the'formulaf;

R(OCONHCH2OR..")3. wherein R, representsxthe aliphatic radicalof a,glyceryl compoundselectia ed from the group consisting of castor oil andhy-": drogenated' castor oil and R" is selected from the. groupconsisting of hydrogen and alkane radi-"p'.

calsof from'oneto four carbon atoms.

4. A rocess for the. production of anti-shrinln-i" ing compoundswhichcomprises reacting a tris-z". leinw' The solvent is then-removed-byevap0rationq5= carbamate selected from the groupconsisting of drous.sodium carbonate. ,The mixture is filtered; and the solvent is removedfrom the filtrate by}.

triolein-ll:11':11"-triol-triscarbamate and tristearin-ll :1l' 11'-triol-tris-carbamate with an aldehyde selected from the groupconsisting of formaldehyde and paraformaldehyde.

5. A process as claimed in claim 4 wherein said triscar-bamate istristearin-11:11':11" trioltriscarbamate.

6. A process. as claimed in claim 4 wherein said triscarbamate istriolein-llzll':11"-trio1- triscarbamate.

'7. A process as claimed in claim 4 wherein the reaction is carried outat a temperature of between 40 C. and 60 C.

8. A process as claimed in claim 4 wherein the reaction is carried outin the presence of an inert solvent.

9. A process as claimed in claim 4 wherein the reaction is carried outunder alkaline conditions.

10. A process as claimed in claim 4 wherein the reaction is carried outunder acidic conditions in the presence of a saturated aliphatic alcoholof from 1 to 4 carbon atoms.

11. A process for increasing the shrink-resistance of textiles whichcomprises impregnating the textile material with an acidic emulsion ofa, compound having the formula R(OCONHCH2OR," 3

wherein R represents the aliphatic radical of a glyceryl compoundselected from the group consaid compound.

12. A process as claimed in claim 11 wherein said acidic emulsioncontains a. dispersing agent.

13. A process as claimed in claim 11 wherein said compound istristearin-11:11' :11"-trio1 trismethylol carbamate.

14. A process as claimed in claim 11 wherein said compound istriolein-llz11:11"-triol trismethylol carbamate. 15. A proces as claimedin claim 11 wherein the heating is carried out at a temperature of about145C.

WILLIAM BAIRD. THOMAS BARR. ARTHUR LOWE. JACK OLIVER.

REFERENCES CITED The following references are of record in the file ofthis patent:

FOREIGN PATENTS Country Date France Aug. 3, 1942 Number

1. AS A NEW COMPOUNT, TRISTERIN-11:11'':11"TRIOL TRIS-METHYLOLCARBOMATE.